Solution grade pvc-copolymers prepared by suspension polymerization



United States Patent 3,511,822 SOLUTION GRADE PVC-COPOLYMERS PREPARED BY SUSPENSION POLYMERIZATION Paul Kraft, Yonkers, and Siegfried Altscher, Monsey, N.Y., and William F. Keller, South Yarmouth, Mass, assignors to Staulfer Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Jan. 15, 1968, Ser. No. 697,584

Int. Cl. C08f /24, 15/30 US. Cl. 26087.1 11 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to the preparation of solution grade polyvinyl chloride copolymers by suspension polymerization technique. More particularly, this invention relates to the preparation of vinyl chloride/ vinyl acetate copolymers, characterized by the ability to form clear coating solutions, by suspension polymerization.

The term solution in reference to this category of resins generally refers to the application method for utilizing these resins. -It also, however, in the past has been utilized to identify the polymerization procedure in that they are generally prepared by solution polymerization. These resins are characterized as high quality polymers substantially free from catalyst residue and substantially free from contaminants producing haze and low molecular weight fractions. While the solution grade resins are considerably more expensive than conventional polyvinyl chloride homopolymers, the advantages which they afiord justify the additional expense involved. These resins are permanently internally plasticized thereby eliminating plasticizer extraction and migration problems with attendant film embrittlement. They are frequently used as top coats for plastisols for this reason, although where plasticzer content is not critical small quantities of plasticizer may be added to improve impact resistance. These resins are easily soluble in commercial solvents such as methyl isobutyl ketone and film formation occurs HO Axis Patented May 12, 1970 wood generally plywood for exterior and interior use, as coatings for textiles to provide coated fabrics with supple, soft, plush hand and drape demanded by fashions and wear characteristics, as paper and foil coatings; they find use for decorative markings in inks and linings for hot drink cups. As indicated above, they additionally serve as top coats for highly plasticized vinyl compositions and for rubber in polyurethane foams.

It has been well known and conventional in the art to prepare vinyl chloride/vinyl acetate copolymers and terpolymers by solution techniques to provide resins having exceptional clarity when dissolved in a suitable solvent.

Heretofore, the solution grade resins have been prepared in a solvent which is an expensive technique requiring solvent recovery and additional capital investment. Solvent loss in the recovery steps further reduces the efficiency of the operation. While suspension polymerization techniques have been long known, are more easily run and are less costly, suspension polymerized co polymers invariably contain contaminants, i.e., residual suspending agents and catalyst residue. These contaminants contribute to solution haze when the resin is dissolved in conventional solvents, such as methyl isobutyl ketone and methyl ethyl ketone. When such resin solutions are coated on the substrate and dried, these contaminants cause film cloudiness which is undesirable because of reduced coating effectiveness, film continuity, corrosion resistance, salt spray resistance, water resistance and the like.

In accordance with the provisions of the present invention, solution grade resins which yield clear solutions in conventional solvents and exhibit other properties exhibited by typical solution grade resins prepared via the expensive solution polymerization route are prepared by suspension techniques utilizing methyl cellulose as a suspending agent, a hot-reactive catalyst, and a halogenated chain transfer agent.

By the use of the term hot-reactive catalyst is meant those catalysts having a 10 hour half-life at a temperature below C.

Exemplary of the hot catalysts are: a,a'-azobis (u,'ydimethyl valeronitrile), t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like.

By the term methyl cellulose suspending agent is intended both methyl cellulose per Se and its derivatives, as for example hydroxypropylmethyl cellulose, which are conventionally known in the art. Methyl cellulose products are derived from and have the polymeric backbone of cellulose, a natural carbohydrate that contains a basic repeating structure of anhydroglucose units. The basic structure for methyl cellulose is as follows:

wherein N represents the number of repeating units. Methyl cellulose is conventionally prepared by swelling cellulose fibers obtained from cotton linters or wood pulp by a caustic soda solution to produce alkali cellulose. The alkali cellulose is subsequently treated with methyl chloride yielding the methyl ether of cellulose. The fibrous reaction product is purified and ground to a fine uniform powder or granule. Also intended to be within the definition of methyl cellulose are such derivatives as hydroxypropyl methyl cellulose. This derivative is generally prepared by reacting propylene oxide with methyl 4 cellulose to obtain hydroxypropyl substituents on the vantage that the solvent as in suspension polymerization auhydroglucose units. The substituent group assists in the dissipation of heat. The average molecular (OH)CH3) weight of the polymers as prepared :by the use of solution 5 polymerization are generally lower than those obtained COIIiamS a Secondary y y on the Sechhd caihohby the use of other polymerization techniques and this Such Pmducts geheiaiilf P9 Varying ratios f shell method can be effective in the production of low molecu- Y Y P P Y shhshhihoh meihoxyi Substitution lar weight vinyl halide polymers. However, this process These materials are commercially available. The hydroxy has the drawback that the Solvent must be recovered in propyl methyl cellulose has the formula set forth below: 10 order to ff t necessary emciency required in Formula II mercial practice. Both the suspension polymerization tech- E 01120 CH Ir 0 CH3 H2OCH3 H O N 112011 HOH The methyl cellulose derivatives are available commernique and the solution technique defined above are well cially under the name Methocel, a registered trademark of 25 known in the art. Dow Chemical Company. The process of the present invention is particularly ap- T he term halogenated transfer agent for purposes of plicable to the preparation of vinyl chloride, vinyl acetate the present invention, is defined as a halogenated aliphatic copolymers. These copolyme rs generally contain from hydrocarbon containing from 1 to carbon atoms and about 1 to about by Weight vinyl acetateand preffrom about 1 to about halogen atoms. Included under 30 erably from about 13 to about 20% by weight v nyl the definition of halogen is fluorine, bromine and iodine. acetate. The preferred copolymer range indicated provides Included in the term aliphatic hydrocarbon are the base exceptional coating grade resins. It should be noted also materials methane, ethane, propane, butane, pentane, that the preferred copolymer range indicated above prohexane, heptane, octane, nonane, decane, undecane, dodevldes an excepti nally good balance of properties. As 18 cane, tetradecane, hexadecane, octadecane, eicosane. well known, polyvinyl chloride homopolymer exhibits Exemplary of particularly desirable halogenated hydropoor solubility in coating solvents such as methyl ethyl .carbon chain transfer agents in the present in vcntion are ketone, methyl isobutyl ketone and the like. Vinyl acetate carbon tetrachloride, chloroform, ethyltrichloride, perincreases the solubility but detracts from the tou chloroethylene, 1,2-dichloroethylene, N-butylbromide, 2- 0f the vinyl polymer. Therange specified provides an bromopropane, tetrabromoethane, 1,2-dibromotetrachloexcellent balance of solubility and toughness. roethane, trifiuoro l-chloroethane and the like. While it In Preparing the Vlhyl Chloride/Vinyl afieiaie 1 9 3- is indicated in the foregoing that halogenated hydrocarmeTS in PIOCBSS 0f the Present mvellhoh, the Vinyl bons containing from 1 to 20 carbon atoms can be utilized, Chloride and Y y aceiata are generally used Such that the it is preferred to use halogenated hydrocarbons contain- Vinyl acetate 18 Present 111 a!1 amount 0f h h 13 i0 ing from 1 to 5 carbon atoms inclusive and the preferred fi hhsed O11 g The Q ffiachve catalysis halogen present is chlorine. This preference is dictated on Of this Invention are gehel'aiiy i 111 all amount from availability and performance of these compounds. f' to about 03% y Weight based 1 the In order to place the present invention in the proper welght 0f the monomer and are Preferably Used 111 an perspective, a definition of conventional suspension amount from about 0.07 to about 0.11. The m y polymerization and conventional solution polymerization 1111056 suspending agent is generally used in an amount in believed de ir bl from about 0.03 to about 0.3% by weight based upon Suspension polymerization refers to the polymerization mohomeri material generally available at e of monomer dispersed i a suspension medium which is aqueous solution and 1S utilized as such for convenience. a non-solvent for both the monomer and the polymer, It 15 Preferred, f f 'i h this methyl 0611111086 8115- generally water utilizing normally a monomer soluble Pending agent b6 utilized an amount of from about. initiator. Suspension polymerization takes place within Q09 to about y Weight based P h h i'- The the mono er phase t i i h polymer Solution halogenated chain transfer agent as utilized in this inveninitiator. However, the use of the suspending medium him 15 generally used 111 an amount f from about to about 6.0% by weight based upon the weight of the monomer. It is preferred, however, that this transfer agent be utilized in an amount of from about 0.8 to about 3.0%.

It should be noted that the methyl cellulose suspending agent, the hot reactive catalyst and the halogenated chain transfer agent are all critical in this invention in that if these agents are not used as specified, polymer assists in the dissipation of heat of reaction and therefore the polymerization reaction is easier to control. Suspen- 60 sion polymerization is generally accomplished by dispersing the monomer in the suspending medium either by constant agitation or by the use of a suspending agent or both. Various conventional suspending agents are known to the art. These known suspending agents include gelatin hydroxy methyl cellulose: hYdmXY ethyl cellulose solutions of exceptionally low haze are not obtained. Y Y P PY caiiuiose, y methyl cellulose, tale, The polymerization of this invention is generally cony, P y y alcohol and the iikeducted at a temperature of from about 40 C. to about In distinction sohltiim Polymerization is Process which 7 90 C. although it is preferred to conduct this reaction at Teqllifhs the use of an iiieiii liquid, which is a S01VIlt temperatures of from about 45 C. to about C. While for the monomer compound used in forming the poly the polymerization reaction is generally substantially mer, which solvent may or may not be a solvent for the complete after about seven hours, the time of polymerizaprepared polymer. The catalyst or initiator if used is tion generally runs from about ten to twelve hours to inmonomer soluble. Solution polymerization has the ad- 75 sure adequate polymerization.

The polymerization reaction of this invention is conducted at superatmospheric pressure. This pressure is conveniently the vapor pressure of the vinyl chloride, vinyl acetate monomer composition at the specific temperature employed. For example, at 60 C., a mixture of 85 parts of vinyl chloride to 15 parts vinyl acetate affect a pressure of approximately 120 pounds per square inch. For convenience this pressure temperature composition relationship will be denoted as autogeneous pressure. If desired, however, higher pressures can be utilized by subjecting the reaction to the artificial effects of an inert gas under pressure, such as nitrogen. Such high pressure techniques, however, require the use of specialized equipment and, accordingly, are not preferred.

Attempts to employ other suspending agents such as are conventionally used in suspension polymerization have resulted in resins which do not yield the desired characteristics typified by conventional solution grade resins. This is particularly true in respect to. the haze values exhibited by coatings of such resins. Similarly, the employment of conventional non-hot catalysts fail to produce the desired resins as did the employment of chain transfer agents other than the halogenated hydrocarbons.

In Table I below is illustrated conventional and hot catalyst as defined within the terms of this invention, illustrating both structure and temperature half-life at ten hours.

The ten hour half-life temperature of hot catalysts can be determined by preparing a benzene solution of the catalyst to be evaluated at a concentration of 0.2 mole of catalyst per liter of solvent. Ten milliliters of the catalyst solution are pipetted into test tubes suitably drawn for rapid sealing. The tubes preferably used are 16 by 150 millimeters. The filled tubes which preferably have about 5 milliliters of air space remaining are flushed with dry nitrogen, are sealed and immersed in a silicone oil bath and heated for specified periods of time. The oil bath should be continuously stirred and constant temperatu res should be maintained, preferably within plus or minus 0.1 C. The tubes are thereafter Withdrawn from the oil bath periodically and are cooled rapidly by immersion in ice Water. The contents are analyzed for undecomposed catalyst. Iodiometric and infrared techniques can be employed for the analysis. The iodiometric technique consists of treatment of the organic catalyst solution with an inorganic iodide such as sodium or potassium iodide or aqueous hydriodic acid, followed by titration of the liberated iodine with standard sodium thiosulfate solution. Catalysts resistant to iodide reduction can be assayed through the use of infrared differential analysis. In this analysis, standard molar solutions of each peroxide (0.025 m. to 0.4 m.) are prepared and standard curves of absorptions vs. concentration and dis- TABLE I.-STRUCTURE AND HALF-LIFE (10 HOURS) TEMPERATURE "HOT CATALYSTS Conventional Temperature, Catalyst* Structure io i iiii 1. Benzoyl Peroxide 0 72 ll o o il 2. V820 CH3 CH3 65 HsC( 3N=N( lCHs (IN ON 2,2-azobisisobutyronitrile 3. Lauroyl Peroxide 0 0 H3O(CH2)1u-O-O -(CH2)rnCHs 62 Hot Catalysts 4. Azo-52 H CH3 CH3 CH3 52 CHOHzCN=NC-CHz-Ofi HaC JN CN CH3 a,a-Azobis(an-dimethylva1eronitri1e) 5. Lupersol-ll CH3 0 CH: 57

H3CO-*OPJC -CH3 CH CH3 t-B ntyl peroxypivalate 6. IP]? H30 0 O CH;

CH-O OO%OCfi HaC CH3 Diisopropyl peroxydicarbonate 7. Azo-33 H3O CHa CH3 CH3 33 C-CHz( 3-N=N( )CHzC HaC OCHa (IN ON CH3 OCH;

a,a'-AZObiS(a,'y-dimethy1 'y methoxwaleronitrile) Catalysts 1-3, Conventional; Catalysts 4-7, Hot Catalysts.

8 tance vs. concentration are obtained. The residual catapending agent, hot catalyst is critical as the catalyst and W Concentration can then be read ec ly f th@ a halogenated hydrocarbon is critical in respect to the Spectra of p ly d P ed Samples. chain transfer agent. It will be noted from the values in EXAMPLE 1 the foregoing table that in each of the polymerizations A w l was charged i the n i i p in which the critical materials were present, haze values m were obtained of between 11 and 13. These compare very 020 Part of Dow 1242 Mathew], which is commercial well with commercial solution grade resins utilized as a methylcenulose control having a haze value of 8 and exceptionally better 025 Part sodium bicarbonate (as buffer) than those not having the critical materials having values 4.50 parts carbon tetrachloride transfer agent from 22 to 014 part tertiary butyl peroxypivalate hot catalyst Whafis claimed is! 352,0 parts deionized water 1. A method for the suspension polymerization of vinyl The autoclave was sealed and evacuated and 124 parts chlqridee Yinyl acet ate coPolymer which comprises P f vinyl chloride and 26 pal-ts of vinyl acetate were erlzing vinyl chloride with from about 1 to about 25% charged. The reaction was conducted for a period of 14 by Weight Vinyl acetate in the Presence of from about hours at a temperature of about 60 C. At the end of the to about 03% y Weight based uPoll Weight of monomer reaction time, the polymer sample was recovered, washed of a hot catalyst having a ten hour half-life temperature in cold water and dried. This example was repeated identiof less than 60 C., from about 0.03 to about 0.3% by cally, except that in place of methylcellulose suspending weight based upon monomer of a methyl cellulose susagfint, an equivalent amount of a commercial p i n pending agent and a halogenated aliphatic hydrocarbon gfad gelatin utilimd- The Sample was aflditionally containing from about 1 to about 20 carbon atoms inand drled- The two samples were dlssolve? elusive as a chain transfer agent, at a temperature of methyl lsobutyl ketone to a concentration of 20%. S1m1- from about C. to about Q larly, a sample of commercial solution grade vinyl chloride/vinyl acetate resin of similar composition was dissolved to a similar concentration. The three samples were evaluated for haze value by utilizing a turbidimeter manu- 2. The method of claim 1 wherein the hot catalyst is utilized in an amount of from about 0.07 to about 0.11% by weight, the methyl cellulose suspending agent is utifactured by Hach Chemical Company, No. 1860. Table filed in an amount of from to about 015% 11 b l Shows h results of hi determination weight and the chain transfer agent is a lower alkyl ha- TABLE E lide utilized in an amount of from about 0.8 to about 3.0% by weight. v eiiiie b gilag gfi 3. The method of claim 1 wherein the polymerization gfig g fi g gga is conducted at a temperature of from about 45 to about 75 c.

iSEfitgfifif Ei el flj ffftfi j 11.12 4. The method of claim 1 wherein the hot catalyst utileter 9001181. G

lized is a,oz'-21Z0bi$ (a,'y-dimethyl valeronitrile). VYHHwnmn Gamma) solution 8 9 5. The method of claim 1 wherein the hot catalyst EXAMPLES 2 THRU 8 utilized is tertiary butyl peroxypivalate.

Utilizing the identical procedure as set forth in Exirhefnethod of 6131111 l'wherem the hot Y ample l, polymerization reactions were conducted varyllZed 1S p py p q y f ing the suspending agent, the catalyst and the chain trans- The method of clalm 1 wherein the hot Catalyst lltlfer agent as indicated in Table III below. lized is a, x-azobis (an-dimethyl-'y-methoxyvaleronitrile).

TABLE TIL-EFFECT OF COMPOSITION ON SOLUTION CLARITY All Examples Same as No. 1 Except- 20% MIBK, Example suspending Agent Catalyst Chain Trans. Agent Haze Value 11 e2 22 28 13 13 C614 13 Acetaldehyde 31 1 o. 6 Propionaldehyde 20-22 Control r n Grade VYHN Resin (Union Carbide) 3 From the data provided in the foregoing table, it can 8. The method of claim 1 wherein the suspending agent readily be seen that methyl cellulose is critical as a susutilized is a methyl cellulose having the formula:

III TH (innooin '1 1l T CH 0 no oone n n n /n 0y0 1ie H\ H n H o \on H/ H n \H o1r o L (L 1 0 CHzOOHa H CH3 N CHzOH 9 1 0 wherein N designates the number of repeating units. wherein N designates the number of repeating units.

9. The method of claim 1 wherein the methyl cellulose 10. The method of claim 1 wherein the chain transfer suspending agent has the formula: agent is carbon tetrachloride.

11. The method of claim 1 wherein the chain transfer 5 agent utilized is chloroform.

H OH CHzCOH; E 0011 .01? 1 1 .1 1... H X H \H 0 OH H H H H OH I o L I r L o CH2OCH3 H O N H2OH OH: OHOH References Cited UNITED STATES PATENTS 3,293,119 12/1966 Abercrombie 26017 3,420,807 1/1969 Harrison 26092.8 2,471,959 5/1949 Hunt 26089.5 2,875,186 2/1959 Gerhard et a1. 26092.8 2,951,062 8/1960 Deanin 26087.1 3,375,238 3/1968 Bauer et a1. 26092.8

FOREIGN PATENTS 1,249,525 9/1967 Germany. 1,493,610 7/1967 France.

OTHER REFERENCES Columbia-Southern Technical Bulletin, Columbia- Southern Chem. Corp., 1959, pages 3-5.

JOSEPH L. SCHOFER, Primary Examiner C. A. HENDERSON, JR., Assistant Examiner US. Cl. X.R. 26017, 95

W ge UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,5 Dated y 97 Inventor(s) Paul Kraft et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

T- Column 3 line 37, delete the words "in vention" and in lieu -1 thereof insert the word --invention- Column '5, line 51, delete the word "in' and in lieu thereof insert the word -is-- Column 1-, line 58., delete the numbers 0. O5" and in lieu thereof insert the numbers --O. 5-- Column 4, line 68, after the word "polymerization" insert the word --reaction-- Column 5, Table I Item 6 under heading "Temperature C. Hal f-life 10 hours" the number +6 was omitted; The following portion of the formula in Claim 9 is to read as follows:

. CH OCH W V OH H t H i bag IHOH CH Under the References Cited, Abercrombie Patent No. to read SIGNEUAND SEALED 001201970 emu Anew L. namaunmlv. mm 1:. .m.J

Dominican at Patents Anesting Officer 

